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  • C21D6/00—Heat treatment of ferrous alloys
  • C21D6/005—Heat treatment of ferrous alloys containing Mn
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  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
  • C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
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  • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
  • C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
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  • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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  • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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  • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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  • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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  • C21D2211/00—Microstructure comprising significant phases
  • C21D2211/008—Martensite

Definitions

• the present invention relates to a high-strength seamless steel pipe suitable for use in oil well pipes and line pipes, and more particularly to improvement of resistance to sulfide stress corrosion cracking (SSC resistance) in a wet hydrogen sulfide environment (sour environment). .
• SSC resistance sulfide stress corrosion cracking
• Patent Document 1 discloses a low alloy containing, by weight, C: 0.2 to 0.35%, Cr: 0.2 to 0.7%, Mo: 0.1 to 0.5%, and V: 0.1 to 0.3%.
• a method for producing oil well steel in which steel is quenched at an Ac 3 transformation point or higher and then tempered at 650 ° C. or higher and an Ac 1 transformation point or lower.
• the total amount of precipitated carbide can be adjusted to 2 to 5% by weight, and the proportion of MC type carbide in the total amount of carbide can be adjusted to 8 to 40% by weight. It is said that oil well steel having excellent resistance to sulfide stress corrosion cracking can be obtained.
• Patent Document 2 discloses a low alloy containing, by mass, C: 0.15 to 0.3%, Cr: 0.2 to 1.5%, Mo: 0.1 to 1%, V: 0.05 to 0.3%, and Nb: 0.003 to 0.1%. After the steel is heated to 1150 ° C or higher, the hot working is finished at 1000 ° C or higher and subsequently quenched from 900 ° C or higher, then tempered at 550 ° C or higher and below the Ac 1 transformation point, and further 850-1000 ° C.
• a method for producing steel for oil wells that is excellent in toughness and resistance to sulfide stress corrosion cracking, which is subjected to quenching and tempering at least once after quenching by reheating to 600 ° C and below the Ac 1 transformation point.
• the total amount of precipitated carbide is 1.5 to 4% by mass, and the proportion of MC type carbide in the total amount of carbide is 5 to 45% by mass.
• M 23 C 6 type carbide This ratio can be adjusted to 200 / t (t: wall thickness (mm)) mass% or less, and it is said that the oil well steel is excellent in toughness and resistance to sulfide stress corrosion cracking.
• Patent Document 3 by mass, C: 0.15 to 0.30%, Si: 0.05 to 1.0%, Mn: 0.10 to 1.0%, P: 0.025% or less, S: 0.005% or less, Cr: 0.1 to 1.5 %, Mo: 0.1 to 1.0%, Al: 0.003 to 0.08%, N: 0.008% or less, B: 0.0005 to 0.010%, Ca + O (oxygen): 0.008% or less, Ti: 0.005 to 0.05%, Nb: Containing one or more of 0.05% or less, Zr: 0.05% or less, V: 0.30% or less, the maximum length of continuous non-metallic inclusions by cross-sectional observation is 80 ⁇ m or less, non-metal by cross-sectional observation Oil well steels in which the number of inclusions having a particle size of 20 ⁇ m or more is 10/100 mm 2 or less have been proposed. Thereby, it is said that a low alloy steel material for oil wells having high strength required for oil wells and excellent SSC resistance
• Patent Document 4 in mass%, C: 0.20 to 0.35%, Si: 0.05 to 0.5%, Mn: 0.05 to 0.6%, P: 0.025% or less, S: 0.01% or less, Al: 0.005 to 0.100 %, Mo: 0.8 to 3.0%, V: 0.05 to 0.25%, B: 0.0001 to 0.005%, N: 0.01% or less, O: 0.01% or less and sulfide stress corrosion resistance satisfying 12V + 1-Mo ⁇ 0 Low alloy oil well pipe steels with excellent cracking properties have been proposed.
• Cr 0.6% or less may be contained by mass% so as to satisfy Mo ⁇ (Cr + Mn) ⁇ 0, and Nb: 0.1 % Or less, Ti: 0.1% or less, Zr: 0.1% or less may be contained, and Ca: 0.01% or less may be contained.
• Patent Documents 1 to 4 alone is a high-strength seamless that exceeds YS: 125 ksi (862 MPa) class. It cannot be said that it is sufficient as a technique for improving the SSC resistance of steel pipes to characteristics sufficient for oil wells used in severe corrosive environments. Moreover, it is very important to stably adjust the type and amount of carbides described in Patent Documents 1 and 2 and the shape and number of non-metallic inclusions described in Patent Document 3 within a desired range. There is also the problem that it is difficult.
• An object of the present invention is to solve the problems of the prior art and to provide a high-strength seamless steel pipe for oil wells excellent in sulfide stress corrosion cracking resistance and a method for producing the same.
• “high strength” here refers to the case where the yield strength YS is 125 ksi (862 MPa) or more.
• “excellent in resistance to sulfide stress corrosion cracking” as used herein means 5.0 mass by which 10 kPa of hydrogen sulfide is saturated and the pH is adjusted to 3.5 in accordance with the test method specified in NACE TM0177 Method A. A constant load test was performed in an acetic acid-sodium acetate aqueous solution (liquid temperature: 24 ° C) containing a 1% sodium chloride aqueous solution, and cracking exceeded 720 h (hours) with a stress of 85% of the yield strength of the material under test. The case where no occurs.
• Nitride inclusions with a particle size of 4 ⁇ m or more and oxide inclusions with a particle size of 4 ⁇ m or more are the starting points of sulfide stress corrosion cracking (SSC). The larger the size, the more likely SSC is generated. I found out.
• Nitride inclusions having a particle size of less than 4 ⁇ m do not become the starting point of SSC even if they are present alone, but if they become a large number, they will adversely affect SSC resistance, and less than 4 ⁇ m It has been found that a large number of oxide inclusions adversely affects SSC resistance.
• the inventors reduced the number of nitride inclusions and oxide inclusions to an appropriate number or less depending on the size. I came up with the need to adjust.
• the amount of N and O in the production of steel pipe materials, especially during the melting and casting of molten steel, etc. It is important to control so that the value falls within the desired range. Furthermore, it is important to manage manufacturing conditions in the steel refining process and the continuous casting process.
• the present invention has been completed based on such findings and further studies. That is, the gist of the present invention is as follows. (1) By mass%, C: 0.20 to 0.50%, Si: 0.05 to 0.40%, Mn: 0.3 to 0.9%, P: 0.015% or less, S: 0.005% or less, Al: 0.005 to 0.1%, N: 0.006 %, Mo: 1.0% to 3.0%, V: 0.01% to less than 0.05%, Nb: 0.001% to less than 0.01%, B: 0.0003 to 0.0030%, O (oxygen): 0.0030% or less, Ti: 0.003 to It contains 0.025% and contains Ti and N so as to satisfy Ti / N: 2.0 to 5.0, and has a composition comprising the balance Fe and inevitable impurities, and tempered martensite is 95% or more by volume.
• the prior austenite grains have a grain size number of 8.5 or more, and nitride inclusions with a grain size of 4 ⁇ m or more per 100 mm 2 and nitride inclusions with a grain size of less than 4 ⁇ m things 100 mm 2 per 1000 or less, particle size 4 ⁇ m or more oxide inclusions is 100 mm 2 per 40 or less, the particle size is oxide inclusions of less than 4 ⁇ m is 100 mm 2 per 400 or less tissue
• a yield strength YS: high strength seamless steel pipe for oil well is 862MPa or more.
• a method for producing a high-strength seamless steel pipe for oil wells that is tempered by heating to a temperature.
• the steel is reheated to a temperature in the range of Ac 3 transformation point to 1000 ° C. and rapidly cooled to a temperature of 200 ° C. or less at the surface temperature.
• a method for producing a high-strength seamless steel pipe for oil wells that is subjected to quenching treatment at least once.
• a high strength seamless steel pipe for oil wells having a high yield strength YS: 125 ksi (862 MPa) or more and excellent sulfide stress corrosion cracking resistance can be easily and inexpensively manufactured. There are remarkable effects in the industry.
• by containing an appropriate amount of an appropriate alloy element and suppressing the formation of nitride inclusions and oxide inclusions desired high strength for oil wells and excellent SSC resistance can be obtained.
• the high-strength seamless steel pipe to hold can be manufactured stably.
• C 0.20 to 0.50% C dissolves and contributes to increasing the strength of the steel, improves the hardenability of the steel, and contributes to the formation of a structure whose main phase is the martensite phase during quenching. In order to obtain such an effect, the content of 0.20% or more is required. On the other hand, if the content of C exceeds 0.50%, cracking occurs during quenching, and the productivity is significantly reduced. For this reason, the C content is limited to the range of 0.20 to 0.50%. Preferably, the C content is 0.20 to 0.35%. More preferably, the C content is 0.24 to 0.32%.
• Si 0.05 to 0.40%
• Si is an element that acts as a deoxidizer, has a function of increasing the strength of the steel by solid solution in the steel, and further suppressing softening during tempering. In order to acquire such an effect, it is necessary to contain Si 0.05% or more.
• a large amount of Si exceeding 0.40% promotes the formation of a ferrite phase that is a softening phase, inhibits the desired high strength, and further promotes the formation of coarse oxide inclusions, Reduces SSC resistance and toughness.
• Si is an element that segregates and locally hardens the steel, and a large content exceeding 0.40% has a bad effect of forming a locally hardened region and lowering the SSC resistance. Therefore, in the present invention, the Si content is limited to the range of 0.05 to 0.40%.
• the Si content is 0.05 to 0.30%. More preferably, the Si content is 0.24 to 0.30%.
• Mn 0.3-0.9%
• Mn is an element that improves the hardenability of steel and contributes to an increase in steel strength. In order to acquire such an effect, Mn needs to contain 0.3% or more.
• Mn is an element that segregates and locally hardens the steel, and the inclusion of a large amount of Mn has an adverse effect of forming a local hardening region and lowering the SSC resistance. Therefore, in the present invention, the Mn content is limited to the range of 0.3 to 0.9%. Preferably, the Mn content is 0.4 to 0.8%.
• P 0.015% or less
• P is an element that not only segregates at grain boundaries to cause grain boundary embrittlement but also segregates and locally hardens steel.
• P is an inevitable impurity as much as possible. It is preferable to reduce it, but up to 0.015% is acceptable. For this reason, the P content is limited to 0.015% or less. Preferably, the P content is 0.012% or less.
• S 0.005% or less S is an unavoidable impurity, most of which is present as sulfide inclusions in steel, and lowers ductility, toughness and SSC resistance. Up to 0.005% is acceptable. For this reason, S content was limited to 0.005% or less. Note that the S content is preferably 0.003% or less.
• Al acts as a deoxidizer and combines with N to form AlN, contributing to the refinement of austenite grains during heating.
• Al fixes N and prevents solute B from binding to N, thereby suppressing the reduction of the effect of improving the hardenability of B.
• Al needs to contain 0.005% or more.
• the content of Al exceeding 0.1% causes an increase in oxide inclusions, lowers the cleanliness of the steel, and leads to a decrease in ductility, toughness and SSC resistance. Therefore, the Al content is limited to the range of 0.005 to 0.1%.
• the Al content is 0.01 to 0.08%. More preferably, the Al content is 0.02 to 0.05%.
• N 0.006% or less N is present in steel as an unavoidable impurity, but it combines with Al to form AlN, and also combines with Ti to form TiN to refine crystal grains and improve toughness. Has the effect of improving. However, if the content exceeds 0.006%, the formed nitride becomes coarse, and the SSC resistance and toughness are significantly reduced. For this reason, N was limited to 0.006% or less.
• Mo more than 1.0% and less than 3.0%
• Mo is an element that forms carbides and contributes to strengthening steel by precipitation strengthening, and is effective in securing desired high strength after reducing dislocation density by tempering. Contribute to. SSC resistance is improved by reducing the dislocation density. Mo dissolves in the steel and segregates at the prior austenite grain boundaries, contributing to the improvement of SSC resistance. Furthermore, Mo has an action of densifying the corrosion product and further suppressing the generation and growth of pits that are the starting points of cracks. In order to acquire such an effect, Mo needs to contain more than 1.0%.
• the content of Mo exceeding 3.0% promotes the formation of acicular M 2 C precipitates and, in some cases, the Laves phase (Fe 2 Mo), and decreases the SSC resistance.
• the Mo content is limited to the range of more than 1.0% and not more than 3.0%.
• the Mo content is 1.45 to 2.5%.
• V 0.01% or more and less than 0.05%
• V is an element that forms carbides and carbonitrides and contributes to strengthening of steel. In order to acquire such an effect, V needs to contain 0.01% or more. On the other hand, even if it contains 0.05% or more of V, the effect is saturated and an effect commensurate with the content cannot be expected, which is economically disadvantageous. For this reason, the V content is limited to a range of 0.01% or more and less than 0.05%.
• Nb 0.001% or more and less than 0.01%
• Nb forms carbides and / or carbonitrides, contributes to increasing the strength of the steel by precipitation strengthening, and also contributes to refinement of austenite grains. In order to acquire such an effect, Nb needs to contain 0.001% or more.
• Nb precipitates are likely to be a propagation path for SSC (sulfide stress corrosion cracking), and the presence of a large amount of Nb precipitates based on a large amount of Nb content of 0.01% or more is particularly high strength with yield strength of 125 ksi or more. In steel, this leads to a significant decrease in SSC resistance.
• the Nb content is limited to 0.001% or more and less than 0.01% from the viewpoint of achieving both desired high strength and excellent SSC resistance.
• B 0.0003 to 0.0030% B segregates at the austenite grain boundaries and suppresses the ferrite transformation from the grain boundaries, thereby having the effect of enhancing the hardenability of the steel even when contained in a small amount.
• B needs to contain 0.0003% or more.
• B when B is contained in excess of 0.0030%, it precipitates as carbonitride and the like, the hardenability is lowered, and thus the toughness is lowered.
• the B content is limited to the range of 0.0003 to 0.0030%.
• the B content is 0.0007 to 0.0025%.
• O (oxygen) 0.0030% or less
• O (oxygen) exists as an oxide inclusion in steel as an inevitable impurity. Since these inclusions become the starting point of SSC generation and reduce SSC resistance, in the present invention, it is preferable to reduce O (oxygen) as much as possible. However, excessive reduction leads to higher refining costs, so up to 0.0030% is acceptable. For this reason, O (oxygen) content was limited to 0.0030% or less. In addition, Preferably, O content is 0.0020% or less.
• Ti 0.003-0.025%
• Ti combines with N during solidification of molten steel and precipitates as fine TiN, which contributes to the refinement of austenite grains by its pinning effect.
• Ti needs to contain 0.003% or more.
• TiN becomes coarse and the above-described pinning effect cannot be exhibited, but the toughness is reduced.
• the coarser TiN causes the SSC resistance to decrease. For these reasons, the Ti content is limited to the range of 0.003 to 0.025%.
• Ti / N 2.0-5.0 If Ti / N is less than 2.0, the fixation of N is insufficient, BN is formed, and the effect of improving hardenability by B decreases. On the other hand, when Ti / N is larger than 5.0, the tendency of TiN to become coarse becomes remarkable, and toughness and SSC resistance are lowered. For this reason, Ti / N was limited to the range of 2.0 to 5.0. Preferably, Ti / N is 2.5 to 4.5.
• the above components are basic components, but in addition to the basic composition, the selected elements are selected from Cr: 0.6% or less, Cu: 1.0% or less, Ni: 1.0% or less, W: 3.0% or less. 1 type, 2 or more types, and / or Ca: 0.0005-0.0050% can be contained.
• Cr is an element that increases the strength of steel through the improvement of hardenability and improves the corrosion resistance.
• Cr is an element that combines with C during tempering to form carbides such as M 3 C, M 7 C 3 , and M 23 C 6 (M is a metal element), and improves temper softening resistance. .
• M is a metal element
• Cr is desirably contained in an amount of 0.10% or more.
• the Cr content exceeds 0.6%, a large amount of M 7 C 3 and M 23 C 6 is formed, which acts as a hydrogen trap site and lowers the SSC resistance. For this reason, when it contains Cr, it is preferable to limit Cr content to 0.6% or less.
• Cu is an element that contributes to increasing the strength of steel and has the effect of improving toughness and corrosion resistance. In particular, it is an extremely effective element for improving SSC resistance in severe corrosive environments.
• Cu When Cu is contained, a dense corrosion product is formed and the corrosion resistance is improved, and further, the generation and growth of pits as the starting point of cracking are suppressed.
• it is desirable to contain Cu 0.03% or more.
• Cu even if Cu is contained in an amount exceeding 1.0%, the effect is saturated, and an effect commensurate with the content cannot be expected, which is disadvantageous for economic efficiency. For this reason, when it contains Cu, it is preferable to limit Cu to 1.0% or less.
• Ni is an element that contributes to increasing the strength of steel and further improves toughness and corrosion resistance. In order to acquire such an effect, it is desirable to contain Ni 0.03% or more. On the other hand, even if Ni is contained in an amount exceeding 1.0%, the effect is saturated, and an effect commensurate with the content cannot be expected, which is disadvantageous for economic efficiency. For this reason, when it contains Ni, it is preferable to limit Ni content to 1.0% or less.
• W is an element that forms carbides and contributes to increasing the strength of the steel by precipitation strengthening, and also dissolves and segregates at the prior austenite grain boundaries to contribute to the improvement of SSC resistance.
• W preferably contains 0.03% or more.
• W content it is preferable to limit W content to 3.0% or less.
• Ca 0.0005 to 0.0050%
• Ca is an element that combines with S to form CaS and effectively acts to control the morphology of sulfide inclusions, and to improve toughness and SSC resistance through the morphology control of sulfide inclusions. Contribute. In order to acquire such an effect, Ca needs to contain 0.0005% or more. On the other hand, even if Ca is contained in excess of 0.0050%, the effect is saturated and an effect commensurate with the content cannot be expected, which is disadvantageous in terms of economy. For this reason, when Ca is contained, the Ca content is preferably limited to a range of 0.0005 to 0.0050%.
• the balance other than the above components is composed of Fe and inevitable impurities.
• unavoidable impurities Mg: 0.0008% or less, Co: 0.05% or less are acceptable.
• the high-strength seamless steel pipe of the present invention has the above-described composition, and further has a volume ratio of 95% or more with tempered martensite as the main phase, the prior austenite grains have a particle size number of 8.5 or more, and in the rolling direction.
• the number of nitride inclusions with a particle size of 4 ⁇ m or more is 100 or less per 100 mm 2
• the particle size is less than 1000 nitride inclusions with a size of less than 4 ⁇ m per 100 mm 2
• the particle size is 4 ⁇ m or more -based inclusions 100 mm 2 per 40 or less
• particle size: oxide inclusions of less than 4 ⁇ m has a tissue is 100 mm 2 400 per below.
• Tempered martensite phase 95% or more
• the main phase is a tempered martensite phase tempered.
• the term “main phase” as used herein refers to a phase in which the phase is a single phase having a volume ratio of 100%, or the phase containing the second phase is 5% or less in a range that does not affect the characteristics. Is the case where the ratio is 95% or more.
• examples of the second phase include a bainite phase, a retained austenite phase, pearlite, or a mixed phase thereof.
• the above structure of the high-strength seamless steel pipe of the present invention can be adjusted by appropriately selecting the heating temperature at the time of quenching according to the steel components and the cooling rate at the time of cooling.
• Particle size number of prior austenite grains 8.5 or more If the particle size number of prior austenite grains is less than 8.5, the substructure of the martensite phase produced becomes coarse and SSC resistance decreases. For this reason, the particle size number of the prior austenite grains is limited to 8.5 or more. As the particle number, a value measured in accordance with JIS G 0551 is used.
• the particle size number of the prior austenite grains can be adjusted by changing the heating rate, heating temperature and holding temperature in the quenching process, and the number of times of quenching process.
• the number of nitride inclusions and oxide inclusions is adjusted within an appropriate range in accordance with the size in order to improve SSC resistance.
• the nitride inclusions and oxide inclusions are identified by automatic detection using a scanning electron microscope.
• the nitride inclusions are mainly composed of Ti and Nb, and oxide inclusions. Is composed mainly of Al, Ca, and Mg.
• the number of inclusions is a value measured in a cross section perpendicular to the rolling direction of the steel pipe (cross section perpendicular to the pipe axis direction: C cross section).
• the particle size of each inclusion is used as the size of the inclusion.
• the particle size of the inclusions was obtained by calculating the equivalent circle diameter by obtaining the area of the inclusion particles and calculating the equivalent particle diameter.
• Nitride inclusions with a grain size of 4 ⁇ m or more 100 or less per 100 mm 2
• Nitride inclusions are the origin of SSC in high-strength steel pipes with a yield strength of 125 ksi or more, and the size is as large as 4 ⁇ m or more. The worse, the worse it is. For this reason, it is desirable to reduce the number of nitride inclusions having a particle size of 4 ⁇ m or more as much as possible, but if the number is 100 or less per 100 mm 2 , an adverse effect on SSC resistance can be tolerated. Therefore, the number of nitride inclusions having a particle size of 4 ⁇ m or more is limited to 100 or less per 100 mm 2 . The number is preferably 84 or less.
• Nitride inclusions with a particle size of less than 4 ⁇ m 1000 or less per 100 mm 2
• Fine nitride inclusions with a particle size of less than 4 ⁇ m are not the origin of SSC even if they exist alone, but yield strength
• the number of high-strength steel pipes of 125 ksi class or higher increases, and if the number exceeds 1000 per 100 mm 2 , the adverse effect on SSC resistance becomes unacceptable. For this reason, the number of nitride inclusions having a particle size of less than 4 ⁇ m is limited to 1000 or less per 100 mm 2 .
• the number is preferably 900 or less.
• Oxide inclusions with a particle size of 4 ⁇ m or more 40 or less per 100 mm 2
• High strength steel pipes are the origin of SSC, and the size is 4 ⁇ m or more The larger the value, the greater the adverse effect. Therefore, it is desirable to reduce the number of oxide inclusions having a particle size of 4 ⁇ m or more as much as possible, but if the number is 40 or less per 100 mm 2 , an adverse effect on SSC resistance can be tolerated. For this reason, the number of oxide inclusions having a particle size of 4 ⁇ m or more is limited to 40 or less per 100 mm 2 . The number is preferably 35 or less.
• Oxide inclusions with a grain size of less than 4 ⁇ m 400 or less per 100 mm 2
• Oxide inclusions are the origin of SSC even if the grain size is less than 4 ⁇ m for high strength steels with yield strength of 125 ksi or higher.
• the adverse effect on SSC resistance increases. Therefore, it is desirable to reduce the oxide inclusions having a particle diameter of less than 4 ⁇ m as much as possible, but it is acceptable if the number is 400 or less per 100 mm 2 .
• the number of oxide inclusions having a particle size of less than 4 ⁇ m was limited to 400 or less per 100 mm 2 .
• Preferably it is 365 or less.
• the ladle from the ladle to the tundish is reduced so that the number of nitride inclusions and oxide inclusions is less than the number per unit area described above.
• sealing with an inert gas is performed, and electromagnetic stirring is performed in the mold to achieve floating separation of inclusions.
• the steel pipe material having the above composition is heated and hot-worked to obtain a seamless steel pipe having a predetermined shape.
• the steel pipe material used in the present invention is prepared by melting molten steel having the above composition by a conventional melting method such as a converter, and by a conventional casting method such as a continuous casting method. It is preferable to do.
• the slab may be further hot-rolled to obtain a round steel piece having a predetermined shape, or a round steel piece that has undergone ingot-bundling rolling.
• the number of nitride inclusions and oxide inclusions is reduced so as to be equal to or less than the above number per unit area. To do. For this reason, it is necessary to reduce the steel pipe material (slab or steel slab) as much as possible within the ranges of N (nitrogen): 0.006% or less and O (oxygen): 0.0030% or less.
• the heat stirring and refining treatment has a treatment time of 30 min or longer and the RH vacuum degassing treatment has a treatment time of 20 min or longer.
• the ladle from the ladle to the tundish is reduced so that the number of nitride inclusions and oxide inclusions is less than the number per unit area described above.
• the slab (steel pipe material) having the above composition is heated to a heating temperature of 1050 to 1350 ° C. and hot-worked to obtain a seamless steel pipe having a predetermined size.
• Heating temperature 1050-1350 ° C
• the heating temperature is less than 1050 ° C.
• the dissolution of carbides in the steel pipe material becomes insufficient.
• the heating temperature is higher than 1350 ° C.
• the crystal grains are coarsened, precipitates such as TiN precipitated during solidification are coarsened, and cementite is coarsened, so that the toughness is lowered.
• a high temperature exceeding 1350 ° C. is not preferable from the viewpoint of energy saving because the scale of the slab surface is formed thick and causes surface flaws during rolling and increases energy loss.
• the heating temperature was limited to a temperature in the range of 1050 to 1350 ° C.
• the temperature is preferably 1100 to 1300 ° C.
• the heated steel pipe material is then subjected to hot working (pipemaking) using a Mannesmann-plug mill type or Mannesmann-mandrel type hot rolling mill to obtain a seamless steel pipe having a predetermined dimension.
• a Mannesmann-plug mill type or Mannesmann-mandrel type hot rolling mill to obtain a seamless steel pipe having a predetermined dimension.
• it is good also as a seamless steel pipe by the hot extrusion by a press system.
• the obtained seamless steel pipe is subjected to a cooling process of cooling at a cooling rate of air cooling or higher until the surface temperature becomes 200 ° C. or lower after the hot working is finished.
• Cooling treatment after completion of hot working cooling rate; air cooling or higher, cooling stop temperature: 200 ° C. or lower
• cooling rate higher than air cooling after hot working
• the martensite phase becomes the main phase.
• the transformation may not be completely completed. Therefore, in the cooling process after hot working, cooling is performed at a cooling rate equal to or higher than air cooling until the surface temperature becomes 200 ° C. or lower.
• the “cooling rate higher than air cooling” refers to 0.1 ° C./s or higher. When the cooling rate is less than 0.1 ° C./s, the metal structure after cooling becomes non-uniform, and the metal structure after the subsequent heat treatment becomes non-uniform.
• ⁇ Temperature treatment is performed after cooling at a cooling rate higher than air cooling.
• the tempering process is a process of heating to a temperature in the range of 600 to 740 ° C.
• Tempering temperature 600-740 °C
• the tempering treatment is performed for the purpose of reducing dislocation density and improving toughness and SSC resistance. If the tempering temperature is less than 600 ° C., the reduction of dislocations is insufficient, so that excellent SSC resistance cannot be ensured. On the other hand, when the temperature exceeds 740 ° C., the tissue is remarkably softened and the desired high strength cannot be ensured. For this reason, the tempering temperature was limited to the range of 600 to 740 ° C.
• the tempering temperature is preferably 660 to 740 ° C. More preferably, it is 670 to 710 ° C.
• Reheating temperature for quenching treatment Ac 3 transformation point or more and 1000 ° C or less If the reheating temperature is less than Ac 3 transformation point, it will not be heated to the austenite single phase region, so a structure with martensite phase as the main phase can be obtained. Absent. On the other hand, when the temperature exceeds 1000 ° C., in addition to coarsening of crystal grains and lowering toughness, there are adverse effects such as thickening of the surface oxide scale, easy peeling and causing wrinkling on the surface of the steel sheet. Furthermore, the load on the heat treatment furnace becomes excessive, which causes a problem from the viewpoint of energy saving. For these reasons and from the viewpoint of energy saving, the reheating temperature for quenching is limited to the Ac 3 transformation point or higher and 1000 ° C. or lower. In addition, Preferably it is 950 degrees C or less.
• Cooling in the quenching treatment is preferably performed by water cooling at an average cooling rate of 2 ° C / s or higher to a temperature of 400 ° C or less at the center position of the plate thickness, until the surface temperature becomes 200 ° C or lower, preferably 100 ° C or lower It is preferable to cool to a temperature of The quenching process may be repeated twice or more.
• a tempering process may be performed to correct a defective shape of the steel pipe in a warm or cold manner as necessary.
• the hot metal discharged from the blast furnace was desulfurized and dephosphorized in the hot metal pretreatment, decarburized and dephosphorized in the converter, and as shown in Table 2, the heat treatment and refining treatment (LF ) And RH vacuum degassing treatment with a reflux rate of 120 ton / min and a treatment time of 10 to 40 min to obtain molten steel having the composition shown in Table 1, and a slab (round slab: 190 mm ⁇ ) by a continuous casting method.
• tundish Ar gas shielding was carried out except for P steel and S steel, and electromagnetic stirring was carried out in the mold other than N steel and S steel.
• the obtained slab was placed in a heating furnace as a steel pipe material, heated to the heating temperature shown in Table 2, and held (holding time: 2 h).
• the heated steel pipe material was hot-worked using a Mannesmann-plug mill type hot rolling mill to obtain a seamless steel pipe (outer diameter 100 to 230 mm ⁇ ⁇ thickness 12 to 30 mm).
• it air-cooled and the quenching tempering process was performed on the conditions shown in Table 2. In some cases, after hot working, it was cooled with water, and then tempered or quenched and tempered.
• a test piece was collected from the obtained seamless steel pipe and subjected to a structure observation, a tensile test, and a sulfide stress corrosion cracking test.
• the test method was as follows. (1) Microstructure observation From the obtained seamless steel pipe, a specimen for microstructural observation was taken from the inner side 1/4 t position (t: pipe thickness), and the cross section (C cross section) perpendicular to the longitudinal direction of the pipe was polished. Corrosion (Nital (nitric acid-ethanol mixed solution) corrosion) reveals the tissue, and the tissue is revealed using an optical microscope (magnification: 1000 times) and a scanning electron microscope (magnification: 2000 to 3000 times). Observed and imaged at 4 or more fields of view. Based on the obtained tissue photographs, the identification of phases constituting the phases and the tissue fractions of these phases were calculated by image analysis.
• the prior austenite ( ⁇ ) particle size was measured using a structure observation specimen.
• the cross section (C cross section) perpendicular to the longitudinal direction of the tube of the tissue observation specimen is polished and corroded (picral solution (picral (picral acid-ethanol mixed solution)) to reveal the old ⁇ grain boundary, and an optical microscope. (Magnification: 1000 times) was observed, and the field of view was imaged at 3 or more locations.
• tissue photograph the particle size number of the old (gamma) grain was calculated
• the number of particles identified as inclusions was obtained, the area of each particle was obtained, and the equivalent circle diameter was calculated to obtain the particle size of the inclusions. Then, the number density (inclusions / 100 mm 2 ) of inclusions having a particle size of 4 ⁇ m or more and inclusions having a particle size of less than 4 ⁇ m was calculated. Inclusions whose long sides were less than 2 ⁇ m were not analyzed.
• a sulfide stress corrosion cracking test was performed in accordance with the test method specified in NACE TM TM0177 Method A.
• the above-mentioned tensile test piece was tested using the test solution (acetic acid-sodium acetate aqueous solution containing 5.0 mass% saline solution saturated with 10 kPa of hydrogen sulfide and adjusted to pH 3.5 (liquid temperature: 24 ° C. ) Middle), a constant load test is conducted, and a constant load test is held in which a stress of 85% of the yield strength YS is applied. The case where it broke until then was evaluated as “x” (failed). In addition, when the target yield strength could not be secured, the sulfide stress corrosion cracking test was not performed.
• All the examples of the present invention are seamless steel pipes having both high strength of yield strength YS: 862 MPa and excellent SSC resistance.
• the yield strength YS is lowered and the desired high strength cannot be secured, or the SSC resistance is lowered.

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